TWI584068B - Photocurable composition, and methods using the same for forming cured product pattern and for manufacturing optical component, circuit board and imprinting mold - Google Patents

Description

Photocurable composition, and method for forming cured product pattern and manufacturing optical component, circuit board and imprinting mold using the same

The present invention relates to a photocurable composition, and a method of forming a cured product pattern and manufacturing an optical component, a circuit board, and an imprinting mold using the photocurable composition.

In the fields of semiconductor devices, microelectromechanical systems (MEMS), and the like, miniaturization is increasingly required, and thus photon imprint technology has attracted attention.

In the photon imprint technique, a mold having a fine convex pattern on its surface is pressed against a substrate to which a photocurable composition (resist) has been applied, and the light is cured in this state. The composition is cured. Thus, the raised pattern of the mold is transferred to the cured product of the photocurable composition to form a pattern on the substrate. The photon nanoimprint technology enables the formation of fine structures on the substrate in the order of nanometers.

In the photon imprint technique, the resist is first applied to The area on the substrate where the pattern is to be formed (application step). Subsequently, the resist is patterned in a mold having a pattern (mold contact step). Then, the resist is cured by irradiation with light (irradiation step) and separated from the mold (release step). Through these steps, a resin pattern (photocured film) having a specific shape is formed on the substrate.

The cured product pattern (or photocured film) formed on the substrate by the photon nanoimprint technique can be used as a mask for treating the base substrate by dry etching. In this operation, from the viewpoint of treating the base substrate in a high yield, it is desirable that the photocurable composition is resistant to dry etching.

The resistance of the photocurable composition to dry etching (hereinafter referred to as dry etching resistance) depends on the composition of the photocurable composition and its proportion. The viscosity of the photocurable composition also depends on the composition of the photocurable composition and its proportion.

The viscous photocurable composition fills the mold slowly. More specifically, the speed at which the photocurable composition spreads on the substrate when applied to the substrate is slow, or the speed of filling the recess in the fine convex pattern in the mold after contact with the mold slow. Thus, the use of a viscous photocurable composition results in a low productivity of forming a cured product pattern by photon embossing.

Reference list Patent literature

[PTL 1] Japanese Patent Early Publication No. 2007-186570

Accordingly, the present invention provides a photocurable composition that can fill a mold (filling speed) at high speed and has high dry etching resistance.

According to an aspect of the present invention, there is provided a photocurable composition comprising a polymerizable compound (A) and a non-polymerizable component (E), the non-polymerizable component (E) having a weight average molecular weight of 250 or less and The ratio is in the range of 10% by weight to 50% by weight based on the total weight of the polymerizable compound (A) and the non-polymerizable component (E). The polymerizable compound (A) has a parameter of O _A = N _A / (N _{C, A} - N _{O, A} ). N _A represents the total number of atoms in the molecule of the polymerizable compound (A), N _{C, A} represents the number of carbon atoms in the molecule of the polymerizable compound (A), and N _{O, A} represents the polymerizable compound (A) The number of oxygen atoms in the molecule. The non-polymerizable component (E) contains at least one non-polymerizable compound (X) including a photopolymerization initiator (B). The non-polymerizable compound (X) has the parameter O _X =N _X /(N _C,X -N _O,X ). N _X represents the total number of atoms in the molecule of the corresponding compound (X), N _{C, X} represents the number of carbon atoms in the molecule of the corresponding compound (X), and N _{O, X} represents the molecule of the corresponding compound (X) The number of oxygen atoms. The photocurable composition satisfies the following relations (1) and (2): O _A -O _E > 1.00 (1); and O _AE < 3.40 (2).

In these relationships, O _E represents the molar fraction weighted average of the parameter OX of the at least one non-polymerizable compound (X), and O _AE represents the molar fraction weighted average of the parameters O _A and O _E .

Other features of the invention will be apparent from the description of the exemplary embodiments illustrated herein.

101‧‧‧Photocurable composition

102‧‧‧Substrate

103, 105‧‧‧ alignment marks

104‧‧‧Mold

106‧‧·coating film

107‧‧‧Light

108‧‧‧Curing product

109, 110‧‧‧ cured product pattern

111‧‧‧ Section

112‧‧‧Circuit structure

1A] Fig. 1A is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

1B] Fig. 1B is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

1C] Fig. 1C is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

1D] Fig. 1D is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

1E] Fig. 1E is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

1F] Fig. 1F is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

1G] Fig. 1G is a schematic cross-sectional view illustrating a method of forming a cured product pattern according to this embodiment.

Exemplary embodiments of the present invention are described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. Further, the present invention includes any modifications or variations that may be made within the scope and spirit of the invention, which may be made by those skilled in the art.

[Photocurable composition]

The photocurable composition according to an embodiment contains a polymerizable compound (A) which is referred to as component (A); and a photopolymerization initiator (B) which may be referred to as component (B). The photocurable composition of the present embodiment may further contain a non-polymerizable compound (C) which may be referred to as component (C). The photocurable composition is suitable for use in photon imprinting.

As used herein, the term "cured product" refers to a product that undergoes polymerization of a polymerizable compound for curing some or all of the polymerizable compound. To emphasize, a cured product having a very small thickness with respect to its area may be specifically referred to as a cured film. The shape of the cured product or cured film is not particularly limited, and may have a pattern on the surface thereof.

The components of the photocurable composition will be described in detail.

[Component (A): Polymerizable Compound]

Component (A) is a polymerizable compound. The polymerizable compound mentioned herein is reacted with a polymerization factor such as a radical generated from a photopolymerization initiator (component (B)), and thus a polymer film is formed by a chain reaction (polymerization reaction).

The polymerizable compound may be a radical polymerizable compound. The polymerizable compound (or component (A)) may be a single polymerizable compound or a combination of a plurality of polymerizable compounds.

The radically polymerizable compound may have at least one acrylonitrile group or methacryl oxime group, and thus may be a (meth)acrylic compound. Therefore, it is advantageous that the photocurable composition of the present embodiment contains as a constituent The (meth)acrylic compound which is one of the compounds of the component (A), and more preferably the (meth)acrylic compound is the main component of the component (A). Most preferably, component (A) is a (meth)acrylic compound. When the (meth)acrylic compound is the main component of the component (A), the (meth)acrylic compound accounts for 90% by weight or more of the component (A).

If the radically polymerizable compound is a combination of a plurality of compounds each having at least one propylene fluorenyl group or methacryl fluorenyl group, it is advantageous that the radically polymerizable compound contains a monofunctional (meth)acrylic monomer and a polyfunctional ( Methyl) acrylic monomer. A strong cured film can be formed by combining a monofunctional (meth)acrylic monomer and a polyfunctional (meth)acrylic monomer.

Examples of monofunctional (meth)acrylic compounds having an acryloyl or methacryl group include, but are not limited to, phenoxyethyl (meth)acrylate, phenoxy-2-methyl (meth)acrylate Ethyl ethyl ester, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified (meth)acrylic acid to isopropyl Phenylphenolate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-tribromobenzene (meth)acrylate Oxyethyl ester, EO modified phenoxy (meth) acrylate, PO modified phenoxy (meth) acrylate, (meth) acrylate polyoxyethyl phenyl phenyl ether ester, ( Isodecyl methacrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate , (meth) methacrylate, tricyclodecyl (meth) acrylate (tricyclodecanyl (meth)acrylate), dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate , 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy(meth)acrylate Butyl ester, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate Amyl (meth) acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate Isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyl (meth)acrylate Ester hexyl ester, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, eleven (meth) acrylate, dodecyl (meth) acrylate, (methyl) ) Lauryl acrylate and (meth)acrylic acid Ester, isostearyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofuran (meth)acrylate, butoxyethyl (meth)acrylate, ethoxylate (meth)acrylate Ethylene glycol ester, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate , (meth)acrylic methoxypolyethylene glycol ester, (meth)acrylic methoxypolypropylene glycol ester, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide , N,N-dimethyl(meth)acrylamide, third octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Ester, (meth)acrylic acid 7- Amino-3,7-dimethyloctyl ester, N,N-diethyl(meth)acrylamide and N,N-dimethylaminopropyl(meth)acrylamide.

Some monofunctional (meth)acrylic compounds are commercially available, and examples thereof include, but are not limited to, Aronix series M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, and M156 (each Toagosei manufactured); MEDOL 10, MIBDOL 10, CHDOL 10, MMDOL 30, MEDOL 30, MIBDOL 30, CHDOL 30, LA, IBXA, 2-MTA, HPA, and Biscoat series #150, #155, #158, #190, #192,#193,#220,#2000, #2100, and #2150 (each manufactured by Osaka Organic Chemical Industry); Light Acrylates BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA -MPE, HOA-MPL, PO-A, P-200A, NP-4EA and NP-8EA, and epoxy ester M-600A (each manufactured by Kyoeisha Chemical); KAYARAD TC110S, R-564 and R-128H ( Each manufactured by Nippon Kayaku); NK esters AMP-10G and AMP-20G (each manufactured by Shin-Nakamura Chemical); FA-511A, 512A and 513A (each manufactured by Hitachi Chemical); PHE, CEA, PHE-2, PHE -4, BR-31, BR-31M and BR-32 (each manufactured by Dai-ichi Kogyo Seiyaku); VP (manufactured by BASF); and ACMO, DMAA and DMAPAA (each manufactured by Kohjin).

Examples of polyfunctional (meth)acrylic compounds having two or more propylene fluorenyl groups or methacryl fluorenyl groups include, but are not limited to, trimethylolpropane di(meth)acrylate, tris(hydroxy)acrylate Propyl ester, trimethylolpropane tris(meth)acrylate modified by EO, modified by PO Trimethylolpropane (meth)acrylate, trimethylolpropane tris(meth)acrylate modified by EO, PO, dihydroxytricyclodecyl di(meth)acrylate, tris(methyl) Pentaerythritol acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Glycol ester, polypropylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, di(meth)acrylic acid Neopentyl glycol ester, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantane dimethanol (di) Ester, isocyanocyl tris(meth)acrylate bis(2-hydroxyethyl) ester, iso-cyanuric acid ginsyl (propylene oxy) ester, di(meth)acrylic acid bis(hydroxymethyl) three Cyclodecyl ester, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-((meth)propene) modified by EO Oxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy)phenyl)propane modified by PO, and 2,2-bis (4) modified by EO, PO -(( Yl) propenyloxy) phenyl) propane.

Polyfunctional (meth)acrylic compounds are commercially available, and examples thereof include, but are not limited to, Yupimer UV SA1002 and Yupimer UV SA2007 (each manufactured by Mitsubishi Chemical); Biscoat series #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT and 3PA (each manufactured by Osaka Organic Chemical Industry); Light Acrylates 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A and DPE-6A (each manufactured by Kyoeisha Chemical); KAYARAD PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60 and -120 , HX-620, D-310, and D-330 (each manufactured by Nippon Kayaku); Aronix series M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, and M400 (each by Toagosei); And Ripoxy VR-77, Ripoxy VR-60 and Ripoxy VR-90 (each manufactured by Showa Denko).

Among the above compounds, (meth) acrylate means acrylate or methacrylate containing the same alcohol residue as the acrylate. Further, the (meth) acrylonitrile group means an acryl fluorenyl group or a methacryl fluorenyl group containing the same alcohol residue as the acrylonitrile group. EO represents ethylene oxide, and EO-modified compound A is a compound in which (meth)acrylic acid and an alcohol residue of compound A are bonded to each other with an ethylene oxide block structure therebetween. PO represents propylene oxide, and the PO-modified compound B is a compound in which (meth)acrylic acid and an alcohol residue of the compound B are bonded to each other with a propylene oxide block structure therebetween.

[Component (B): Photopolymerization Initiator]

Component (B) is composed of at least one photopolymerization initiator.

The photopolymerization initiator used in the present embodiment senses light having a specific wavelength to produce the above polymerization factor (free radical). More specifically, the photopolymerization initiator is a free radical generating radical generated by light (radiation such as infrared radiation, visible radiation, ultraviolet radiation, extreme ultraviolet radiation, X-ray radiation, and electron beam and other charged particle radiation). Agent.

Component (B) may be a single photopolymerization initiator or a combination of a plurality of photopolymerization initiators.

Exemplary free radical generators include, but are not limited to, substituted or unsubstituted 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimerization , 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2 -(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone and benzophenone derivatives such as N,N'-tetramethyl-4,4'- Diaminobenzophenone (Mitchlerone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylamino group Benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-aminoaromatic ketone derivatives , such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 and 2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinyl-propan-1-one; hydrazine, such as 2-ethyl hydrazine, phenanthrenequinone, 2-tert-butyl fluorene, octamethyl hydrazine, 1,2-benzopyrene , 2,3-benzopyrene, 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10 - phenanthrenequinone, 2-methyl-1,4-naphthoquinone, and 2,3- Methyl hydrazine; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin and benzoin derivatives such as methyl benzoin, ethyl benzoin, and propyl benzoin; benzyl Derivatives such as benzyldimethylketal; acridine derivatives such as 9-phenyl acridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine And N-phenylglycine derivatives; acetophenone and acetophenone derivatives, such as 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2, 2-dimethoxy-2-phenylacetophenone; thioxanthone and thioxanthone derivatives such as diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; a phosphinylphosphine derivative such as 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, and oxidized double- (2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine; an oxime ester derivative such as 1,2-octanedione, 1-[4-(phenylsulfonate) Phenyl-, 2-(o-benzylidene hydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl ]-,1-(o-Ethyl Oxime); and Ketone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy- 2-methyl-1-phenylpropan-1-one.

The free radical generator may be a commercially available one, and examples thereof include, but are not limited to, Irgacure series 184, 369, 651, 500, 819, 907, 784, and 2959, CGI-1700, -1750 and -1850, CG24-61, Darocur series 1116 and 1173, Lucirin TPO, LR 8893, and LR 8970 (each manufactured by BASF); and Ubecryl P36 (manufactured by UCB).

Among them, a fluorenylphosphine oxide-based photopolymerization initiator is suitably used as the component (B). Among the photopolymerization initiators cited above, oxidized 2,4,6-trimethylbenzhydryldiphenylphosphine, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and oxidized double (2,6-Dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine is a phosphinylphosphine-based compound.

The proportion of component (B) (or photopolymerization initiator) in the photocurable composition may be relative to the total weight of component (A) and component (B) and component (C) which will be described below. (ie, the total weight of all components except the solvent) is in the range of 0.1% by weight to 50% by weight. Desirably, it is in the range of 0.1% by weight to 20% by weight, more desirably in the range of more than 10% by weight to 20% by weight.

When the ratio of the component (B) is 0.1% by weight based on the total weight of the components (A), (B) and (C), the photocurable composition can be cured at a high speed; therefore, the reaction efficiency of the compound can be improved. When the ratio of the component (B) is 50% by weight or less based on the total weight of the components (A), (B) and (C), the photocurable composition can form a mechanical strength having a certain degree of mechanical strength. Cured film.

[Component (C): Non-polymerizable compound]

The photocurable composition of the present embodiment may contain, in addition to the components (A) and (B), a non-polymerizable compound as the component (C), depending on the purpose, within the range in which the desired effects of the present invention are produced. Desirably, component (C) is non-volatile. As used herein, the term "non-volatile" means that it is not readily vaporized or dispersed into the air at room temperature under normal pressure. As used herein, the term "volatile" means that it is easily vaporized or dispersed into the air at a temperature ranging from room temperature to 150 ° C under normal pressure. Such a component (C) may be a compound which does not have a polymerizable functional group such as (meth)acrylonitrile group and which cannot sense light having a specific wavelength to produce the above polymerization factor (free radical). Examples of the component (C) include a sensitizer, a hydrogen donor, an internal release agent, a surfactant, an antioxidant, a polymer component, and other additives. Component (C) can be a combination of a plurality of such compounds.

The sensitizer is optionally added to promote the polymerization reaction or to increase the reaction conversion rate. The sensitizer can be a sensitizing dye.

The sensitizing dye is a compound which is excited by absorbing light having a specific wavelength and interacts with a photopolymerization initiator (or component (B)). The term "interaction" as used herein means, for example, the ability of an electron or an electron to be excited. The dye is transferred to the photopolymerization initiator (or component (B)).

Examples of sensitizing dyes include, but are not limited to, anthracene derivatives, anthracene derivatives, anthracene derivatives, anthracene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, Ketone derivatives, coumarin derivatives, thiophene Derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt-based dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, keto-coumarin dyes ,sulfur dye, A dye, an oxonol dye, a cyanine dye, a rose red dye, and a pyrylium salt-based dye.

These sensitizing dyes may be used singly or in combination.

The hydrogen donor is a compound which can react with an initiator radical or a chain terminal radical generated from a photopolymerization initiator (i.e., component (B)) to produce a more reactive radical. Advantageously, the hydrogen donor system is added when the photopolymerization initiator (or component (B)) is a photoradical generator.

Examples of such hydrogen donors include, but are not limited to, amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, second benzylisothiouronium toluenesulfin S-benzylisothiuronium-p-toluene sulfonate, triethylamine, diethylethyl methacrylate, tri-ethyltetramine, 4,4'-bis(dialkylamino)benzophenone , N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl 4-(dimethylamino)benzoate, triethanolamine and N-phenyl Glycine; and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

These hydrogen donors may be used singly or in combination. The hydrogen donor can function as a sensitizer.

An internal release agent can be added to the photocurable composition to reduce the interfacial bonding strength between the mold and the resist, that is, the force for removing the film in the demolding step described below. An internal release agent as referred to herein is a release agent that has been added to the photocurable composition prior to application or placement of the photocurable composition.

The internal release agent can be a surfactant such as a polyoxyxyl surfactant, a fluorosurfactant, or a hydrocarbon surfactant. In this embodiment, the internal release agent is non-polymerizable.

The fluorosurfactant may be a polyalkylene oxide (such as polyethylene oxide or polypropylene oxide) adduct of a perfluoroalkyl alcohol or a polyalkylene oxide of a perfluoropolyether (such as a polycyclic ring). Oxyethane or polypropylene oxide) adduct. The fluorosurfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amine group or a thiol group in one part of the molecule (for example, a terminal group).

The fluorosurfactant can be a commercially available product. Examples of commercially available fluorosurfactants include Megafac series F-444, TF-2066, TF-2067, and TF-2068 (each manufactured by DIC); Fluorad series FC-430 and FC-431 (each manufactured by Sumitomo 3M); Surflon S-382 (manufactured by AGC); EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127 and MF-100 (each manufactured by Tochem Products); PF-636, PF-6320, PF-656 and PF-6520 (each manufactured by OMNOVA Solutions); Unidyne series DS-401, DS-403 and DS-451 (each manufactured by Daikin Industries); and Ftergent series 250, 251, 222F and 208G (each by Neos) Manufacturing).

The internal release agent can be a hydrocarbon surfactant.

The hydrocarbon surfactant may be an alkanol polyalkylene oxide adduct produced by adding an alkylene oxide having 2 to 4 carbon numbers to an alkanol having 1 to 50 carbon numbers.

Examples of the alkanol polyalkylene oxide adduct include a methanol polyethylene oxide adduct, a decyl alcohol polyethylene oxide adduct, a lauryl alcohol ethylene oxide adduct, and a cetyl alcohol polycyclic ring. An oxyethylene adduct, a stearyl alcohol polyethylene oxide adduct, and a stearyl alcohol/polypropylene oxide adduct. The terminal group of the alkanol polyalkylene oxide adduct is not limited to a hydroxyl group, which is formed when an alkylene oxide is simply added to an alkanol. The hydroxyl group can be substituted with a polar functional group such as a carboxyl group, an amine group, a pyridyl group, a thiol group, or a stanol, or a hydrophobic functional group such as an alkyl group or an alkoxy group.

Commercially available alkanol polyalkylene oxide adducts can be used. Examples thereof include polyoxyethylene methyl ether (methanol ethylene oxide adduct) BLAUNON series MP-400, MP-550 and MP-1000 (each manufactured by Aoki Oil Industrial); polyoxyethylene decyl ether (sterol) Ethylene oxide adduct) FINESURF series D-1303, D-1305, D-1307 and D-1310 (each manufactured by Aoki Oil Industrial); polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) BLAUNON EL-1505 (manufactured by Aoki Oil Industrial); polyoxyethylene cetyl ether (cephtanol ethylene oxide adduct) BLAUNON series CH-305 and CH-310 (each manufactured by Aoki Oil Industrial); Polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) BLAUNON series SR-705, SR-707, SR-715, SR-720, SR-730 and SR-750 (each by Aoki Oil Industrial Manufactured; random copolymer type polyoxyethylene/polyoxypropylene stearyl ether BLAUNON series SA-50/50 1000R and SA-30/70 2000R (manufactured by Aoki Oil Industrial); polyoxyethylene methyl ether Pluriol A760E (manufactured by BASF); and polyoxyethylene alkyl ether EMULGEN series (manufactured by Kao).

Among the hydrocarbon surfactants mentioned above, alkanol polyalkylene oxide adducts, especially long chain alkanol polyalkylene oxide adducts, are suitable as internal release agents.

Internal release agents can be used alone or in combination.

The proportion of component (C) (or non-polymerizable compound) in the photocurable composition may be relative to the total weight of components (A), (B) and (C) (ie, all components except solvent) The total weight) is in the range of 0% by weight to 50% by weight. Desirably, it is in the range of 0.1% by weight to 50% by weight, more desirably in the range of more than 0.1% by weight to 20% by weight.

When the ratio of the component (C) is 50% by weight or less based on the total weight of the components (A), (B) and (C), the photocurable composition can form a mechanical strength having a certain degree of mechanical strength. Cured film.

[Ohnishi parameters of each component]

Known dry etching rate of the composition of V, the total number N _O total number N _C of carbon atoms that the composition of, and the oxygen atom of the compositions in the following relation with the composition of the total number of atoms N (3) ( J. Electrochem. Soc., 130, p. 143 (1983)).

V ^OC N/(N _C -N _O ) (3)

The N/(N _C -N _O ) value is known as the "Ohnishi parameter". For example, PTL 1 discloses a photocurable composition that is resistant to dry etching by using a polymerizable compound having a low Ohhishi parameter.

The relation (3) suggests that an organic compound having a small number of oxygen atoms or containing a large number of aromatic ring structures or alicyclic structures has a lower Ohnish parameter and is therefore more resistant to dry etching.

However, polymerizable compounds such as (meth)acrylic compounds tend to have high Ohnishi parameters because the (meth)acrylic group has two oxygen atoms. For example, the Ohnishi parameter of benzyl acrylate (BZA) is relatively low in a monofunctional (meth)acrylic compound of 2.75. For example, the Ohnishi parameter of dihydroxymethyltricyclodecane diacrylate (DCPDA) is relatively low in the polyfunctional (meth)acrylic compound, which is 3.29.

Increasing the number of aromatic rings in the (meth)acrylic compound may be advantageous in reducing the Ohnishi parameter of the (meth)acrylic compound. Unfortunately, increasing the number of aromatic rings increases the molecular weight of the (meth)acrylic compound, thereby increasing the viscosity of the photocurable composition.

Therefore, in the photocurable composition of the present embodiment, a component other than the polymerizable compound (A) in the photocurable composition (that is, a photopolymerization initiator and optionally added as the component (C) Non-polymerizable compounds) have low Ohnishi parameters. In the following description, components (B) and (C) having a low Ohhishi parameter are collectively referred to as a non-polymerizable component (E). As used herein, "non-polymerizable component (E)" is composed of a compound having no polymerizable functional group such as (meth) acrylonitrile.

The non-polymerizable component (E) has a weight average molecular weight of 250 or less. Generally, the lower the molecular weight of the compound in the composition, the lower the viscosity of the composition. By controlling the weight average molecular weight of component (E) to 250 or less, and thus the viscosity of the photocurable composition can be low viscosity.

The presence of the non-polymerizable component as component (E) reduces the Ohnishi parameter of the overall photocurable composition and increases dry etching resistance without substantially increasing the viscosity. Table 1 shows a photopolymerization initiator (component (B)) and a non-polymerizable compound (component (C)) suitable as the component (E).

In the photocurable composition of the present embodiment, the ratio of the non-polymerizable component (E) consisting of a compound having a low Ohhishi parameter is relative to the total of the components (A), (B) and (C). The weight (i.e., relative to the total weight of all compounds except the solvent) is in the range of 10% by weight to 50% by weight. More desirably, it is in the range of 15% by weight to 50% by weight. when When the non-polymerizable component (E) is 10% by weight or more based on the total weight of the components (A) and (E), the Ohnishi parameter of the photocurable composition is entirely lowered, so that the composition can be improved. Dry etching resistance. Further, when the ratio of the non-polymerizable component (E) is 50% by weight or less based on the total weight of the components (A) and (E), the photocurable composition can form a mechanical strength to a certain extent. Cured film.

Further, the photocurable composition of the present embodiment satisfies the following relational expressions (1) and (2): O _A -O _E > 1.00 (1); and O _AE < 3.40 (2).

Such a photocurable composition is highly resistant to dry etching (showing a low dry etch rate).

In these relationships, O _A represents the Ohnishi parameter of the polymerizable compound (A) represented by O _A = N _A /(N _{C, A} -N _{O, A} ). N _A represents the total number of atoms in the polymerizable compound (A), N _{C, A} represents the number of carbon atoms in the polymerizable compound (A), and _{NO, and A} represents an oxygen atom in the polymerizable compound (A). number.

O _{E is} the molar fraction of the Ohnishi parameter O _X of the compound (X) contained in the non-polymerizable component (E). Therefore, O _X =N _X /(N _C,X -N _O,X ). N _X represents the total number of atoms in the molecule of the compound (X), N _{C, X} represents the number of carbon atoms in the molecule of the compound (X), and N _{O, and X} represents the number of oxygen atoms in the molecule of the compound (X).

For example, in the case where the non-polymerizable component (E) contains the compound of M _X1 molar (X1) and the compound of M _X2 molar (X2), the Ohnishi parameter of the non-polymerizable component (E) is OE=(M) _X1 O _X1 + M _X2 O _X2 ) / (M _X1 + M _X2 ).

In the formula, O _X1 =N _X1 /(N _C,X1 -N _O,X1 ) holds. N _X1 represents the total number of atoms in the molecule of the compound (X1), N _{C, X1} represents the number of carbon atoms in the molecule of the compound (X1), and _{NO, and X1} represents the number of oxygen atoms in the molecule of the compound (X1).

In the formula, O _X2 =N _X2 /(N _C,X2 -N _O,X21 ) holds. N _X2 represents the total number of atoms in the molecule of the compound (X2), N _{C, X 2} represents the number of carbon atoms in the molecule of the compound (X 2 ), and _{NO, and X 2} represents the number of oxygen atoms in the molecule of the compound (X 2 ).

If component (A) contains a plurality of polymerizable compounds, the Ohnishi parameter O _{A is} the molar fraction weighted average of the Ohnishi parameters of the plurality of polymerizable compounds.

In the photopolymerizable composition of the present embodiment, the Ohnishi parameter O _{E of the} component (E) (components (B) and (C)) is desirably less than 2.20. Such photopolymerizable compositions can exhibit overall low Ohnishi parameters and are therefore resistant to dry etching.

Advantageously, at least component (B) or component (C) of component (E) consists solely of compounds having a molecular weight of 500 or less. More advantageously, each of the component (B) and the component (C) in the component (E) is composed only of a compound having a molecular weight of 500 or less.

Advantageously, component (E) contains at least one group selected from the group consisting of benzophenone, biphenyl and bistriphenyl. Since the molecular weight of the compounds is 250 or less as shown in Table 1, the weight of the component (E) The average molecular weight can be 250 or less.

The ratio of the components (A) and (B) can be measured by infrared spectroscopy, ultraviolet-visible spectroscopy, pyrolysis gas chromatography mass spectrometry, etc. of the cured film of the photocurable composition or the photocurable composition. . Even when the photocurable composition contains the component (C), the ratio of the components (A), (B) and (C) can be measured by the analysis in the same manner.

[Component (D): Solvent]

The photocurable composition of the present embodiment may further contain a solvent as the component (D). Any solvent can be used as the component (D) as long as it can dissolve the components (A), (B) and (C). Advantageously, component (D) is a volatile solvent having a boiling point in the range of from 80 ° C to 200 ° C at atmospheric pressure. More preferably, the solvent or component (D) has at least one of an ester structure, a ketone structure, a hydroxyl group and an ether structure. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate. They may be used alone or in combination.

The content of the solvent in the photocurable composition may be based on the viscosity of the mixture of the components (A), (B) and (C), the coating method of the photopolymerizable composition, and the thickness of the cured film to be formed. Or other factors to adjust.

However, if the photocurable composition is applied to the substrate by an inkjet method, it is advantageous that the photocurable composition is substantially free of volatile solvents. The term "substantially free of volatile solvents" as used herein means that the photocurable composition does not contain a volatile solvent other than those which inevitably contain as impurities. For example, a volatile solvent in the photocurable composition The content may be 3% by weight or less, such as 1% by weight or less. The photocurable composition containing no volatile solvent does not require a baking step for removing the solvent after application to the substrate, thereby facilitating simplification of the method.

If the photocurable composition of the present embodiment is applied to a substrate by spin coating or the like, the photocurable composition may contain a volatile solvent as the component (D). The solvent in the photocurable composition lowers the viscosity of the photocurable composition, and thus it is advantageous in the case where the coating film of the photocurable composition is formed to a thickness of, for example, 500 nm or less.

[Preparation of Temperature of Photocurable Composition]

In order to prepare the photocurable composition of the present embodiment, at least the components (A) and (B) are mixed and dissolved in each other at a temperature ranging from 0 °C to 100 °C. If component (C) is added, it is mixed and dissolved under the same conditions.

[Viscosity of photocurable composition]

The mixture of the photocurable composition other than the solvent (component (D)) may have a concentration of 1 mPa at 25 ° C. s to 100mPa. The viscosity of the range of s. Preferably, it is tied at 1 mPa. s to 50mPa. The range of s, such as 1mPa. s to 6mPa. The range of s.

The viscosity is 100mPa. The light curable composition of s or lower can fill the recess of the fine pattern in the mold without taking a long time. The use of the photocurable composition enables high productivity light nanoimprinting. Also, it is impossible to cause a filling failure that causes flaws in the formed pattern.

With 1mPa. A light curable composition of s or higher viscosity is more likely to be uniformly applied to the substrate. Moreover, such photocurable compositions do not readily flow out of the mold.

[Surface tension of photocurable composition]

The mixture of the components of the photocurable composition other than the solvent (component (D)) may have a surface tension in the range of 5 mN/m to 70 mN/m at 23 °C. Desirably, it is in the range of 7 mN/m to 35 mN/m, such as 10 mN/m to 32 mN/m. The photocurable composition having a surface tension of 5 mN/m or more can fill the concave portion of the fine pattern in the mold without taking a long time.

Further, the photocurable composition having a surface tension of 70 mN/m or less can form a photocurable film having a smooth surface.

[Impurities in photocurable compositions]

Preferably, the photocurable composition contains as little impurities as possible. Impurities referred to herein are components other than components (A), (B), (C), and (D).

It is therefore preferred that the photocurable composition be purified. For example, filtration through a filter facilitates purification.

In this example, more specifically, a mixture of the components (A) and (B) and the optional component (C) can be filtered through a filter having a pore diameter in the range of 0.001 μm to 5.0 μm. This filtering can be performed in a plurality of steps or repeated several times. The filtrate can be further filtered. Can use multiple Filters with different pore sizes. The filter may be made of polyethylene, polypropylene, fluororesin or nylon, but is not limited thereto.

Impurities such as particulate matter can be removed from the photocurable composition by such filtration. Thus, unintended defects caused by unevenness of particulate matter or other impurities in the cured film formed by curing the photocurable composition can be prevented.

If the photocurable composition of the present embodiment is used for manufacturing a semiconductor integrated circuit, it is desirable to avoid contamination by metal impurities containing metal atoms as much as possible to prevent the metal impurities from interfering with the operation of the product. In such an example, the concentration of the metal impurities in the photocurable composition is preferably 10 ppm or less, more preferably 100 ppb or less.

[Formation of cured product pattern]

A method of forming a cured product pattern (cured film having a pattern) according to an embodiment will be described. 1A to 1G are diagrams illustrating a method of forming a cured product pattern according to this embodiment.

The method for forming a cured product pattern according to this embodiment includes: a first step (1) applying the photocurable composition of the above embodiment, and a second step (2) contacting the photocurable composition with the mold, and third The step (4) irradiates the photocurable composition with light to produce a cured product, and the fourth step (5) separates the cured product from the mold after the third step.

The cured product pattern formed by the method of the present embodiment may be in the range of 1 nm to 10 mm, such as 10 nm to 100 μm. Typically, light is used to form a nanoscale (1 nm to 100 nm) pattern (with bumps) The method of structure) is called photon embossing. The method of forming a cured product pattern incorporates a photon imprint technique.

The program steps of the method will be explained.

[Applying step (1)]

In this step (application step), the photocurable composition 101 is applied (placed) on the substrate 102 as shown in FIG. 1A.

The substrate 102 or treated substrate to which the photocurable composition 101 is applied is typically a tantalum wafer. In order to form an imprint mold using the method of the present embodiment, a quartz substrate can be used as the substrate 102. In this example, a quartz substrate on which a metal compound layer (hard mask material layer) is provided may be used as the substrate 102.

However, the substrate 102 is not limited to a tantalum wafer or a quartz substrate. The substrate 102 may be arbitrarily selected from a substrate for a semiconductor device such as a substrate made of aluminum, a titanium-tungsten alloy, an aluminum-niobium alloy, an aluminum-copper-bismuth alloy, tantalum oxide, or tantalum nitride. The substrate 102 (treated substrate) may be surface treated to increase adhesion to the photocurable composition, such as a decane coupling treatment, a decazane treatment, or an organic film formed thereon.

In this embodiment, the photocurable composition 101 can be, for example, an inkjet method, dip coating, air knife coating, curtain coating, wire barcode method, gravure coating, extrusion A coating, spin coating, or slit scanning process is applied to the substrate 102. In the case of the photon imprint method, the ink jet method is particularly suitable. The thickness of the applied light curable composition to which the pattern will be transferred depends on the application and can be, for example, from 0.01 μm to 100.0 μm. Wai.

[Mold contact step (2)]

Subsequently, as shown in Fig. 1B(b-1), the photocurable composition 101 applied in the previous application step is brought into contact with the mold 104 having the original pattern to be transferred into the desired pattern. Thus, the concave portion of the fine pattern in the surface of the mold 104 is filled with the photocurable composition 101, thus forming the coating film 106 filling the fine pattern of the mold 104 (Fig. 1B (b-2)).

Advantageously, the mold 104 is made of an optically transparent material in view of the subsequent illumination step. Examples of the material of the mold 104 include glass, quartz, optically transparent resin such as polymethyl methacrylate (PMMA) and polycarbonate, transparent metal film formed by vapor deposition, polydimethyl siloxane, etc. A soft film, a photocured film, and a metal film. If an optically transparent resin is used as the material of the mold 104, the optically transparent resin is a material that is insoluble in any component of the photocurable composition 101. Quartz is most suitable as a material for the mold 104 because its coefficient of thermal expansion is small, so that it is impossible to deform the pattern.

The height of the fine pattern in the mold 104 may range from 4 nm to 200 nm, and the aspect ratio of each portion of the pattern may range from 1 to 10.

The mold 104 may be surface treated prior to the mold contacting step to allow the mold 104 to be easily removed from the photocurable composition 101. For the surface treatment, a release agent can be applied to the surface of the mold 104. Examples of the release agent to be applied to the surface of the mold 104 include a polyfluorene detachment agent, fluorine is A release agent for the bottom, a hydrocarbon release agent, a polyethylene-based release agent, a polypropylene-based release agent, a paraffin release agent, a octadecanoic acid release agent, and a carnauba wax release agent. A commercially available release agent of this type of application, such as Optool DSX manufactured by Daikin Industries, can be advantageously used. The release agents can be used singly or in combination. Fluorine-based release agents and hydrocarbon release agents are particularly suitable.

When the photocurable composition 101 is brought into contact with the mold 104 as shown in FIG. 1B(b-1), the pressure applied to the photocurable composition 101 is usually, but not limited to, in the range of 0 MPa to 100 MPa. Preferably, the pressure is in the range of 0 MPa to 50 MPa, more preferably in the range of 0 MPa to 30 MPa, such as in the range of 0 MPa to 20 MPa.

There is no particular limitation on the period during which the mold 104 is kept in contact with the photocurable composition 101. For example, it can range from 0.1 second to 600 seconds. Preferably, it is in the range of 0.1 second to 300 seconds, more preferably in the range of 0.1 second to 180 seconds, such as 0.1 second to 120 seconds.

Although the mold contacting step can be carried out in any atmosphere, such as an atmosphere of air, reduced pressure or an inert gas, it is advantageous from the viewpoint of preventing oxygen or moisture from affecting the curing reaction, that the mold contacting step is under reduced pressure or an inert gas. In progress. The inert gases that can be used in this step include nitrogen, carbon dioxide, helium, argon, chlorofluorocarbon gas, and mixtures of such gases. When the mold contacting step is carried out in an atmosphere of a specific gas (including the case of air), the pressure of the gas may be 0.0001 to 10 atm.

The mold contacting step can be carried out in an atmosphere containing a condensable gas (hereinafter referred to as a condensable gas atmosphere). Condensation mentioned in this article The gas system condenses into a liquid by a capillary generated when the gas fills the recess of the fine pattern in the mold 104 and the gap between the mold and the substrate. The condensable gas is in the form of a gas in the atmosphere before the photocurable composition 101 (the pattern will be transferred to the other) in contact with the mold 104 in the mold contacting step (Fig. 1B(b-1)).

In the mold contacting step performed in the condensable gas atmosphere, the gas that has filled the recess of the fine pattern is converted into a liquid, thereby removing the bubbles. Therefore, the photocurable composition can satisfactorily fill the concave portion of the mold. The condensable gas is soluble in the photocurable composition 101.

The boiling point of the condensable gas is lower than or equal to the temperature of the atmosphere, and is not otherwise limited. For example, it may range from -10 °C to 23 °C, such as from 10 °C to 23 °C. When the boiling point of the condensable gas is within this range, the mold can be satisfactorily filled.

The vapor pressure of the condensable gas at the temperature of the atmosphere in the atmosphere contacting step is lower than or equal to the pressure at which the atmosphere is applied in the atmosphere contacting step, and may be in the range of 0.1 MPa to 0.4 MPa. When the boiling point of the condensable gas is within this range, the mold can be satisfactorily filled. If the vapor pressure is higher than 0.4 MPa at the ambient temperature, the bubbles cannot be removed as expected. Conversely, if the vapor pressure is less than 0.1 MPa at the ambient temperature, decompression is required. This complicates the device.

The temperature of the atmosphere used in the mold contacting step may be, but not limited to, in the range of 20 ° C to 25 ° C.

Examples of the condensable gas include fluorocarbons (FC) including chlorofluorocarbons (CFCs) such as fluoromethane trichloride; hydrofluorocarbons (HFC) and hydrochlorofluorocarbons (HCFC), such as 1, 1,1,3,3-pentafluoropropane (CHF ₂ CH ₂ CF ₃ , HFC-245fa, PFP); and hydrofluoroether (HFE), such as pentafluoroethyl methyl ether (CF ₃ CF) ₂ OCH ₃ , HFE-245mc).

From the viewpoint of satisfactorily filling the mold at the temperature of 20 ° C to 25 ° C in the mold contacting step, it is advantageous to use 1,1,1,3,3-pentafluoropropane (in the case of Vapor pressure at 23 ° C: 0.14 MPa, boiling point: 15 ° C), trichlorofluoromethane (vapor pressure at 23 ° C: 0.1056 MPa, boiling point: 24 ° C) and pentafluoroethyl methyl ether. Particularly advantageous is 1,1,1,3,3-pentafluoropropane because of its high safety.

These condensable gases may be used singly or in combination. The condensable gas can be mixed with a non-condensable gas such as air, nitrogen, carbon dioxide, helium or argon. From the standpoint of satisfactorily filling the mold, ruthenium is more suitable as a non-condensable gas to be mixed with the condensable gas. The crucible can pass through the mold 104. When the gas (condensable gas and helium) fills the concave portion of the fine pattern in the mold 104 together with the coating film 106, the crucible can pass through the mold, and the condensable gas is converted into a liquid.

[Alignment step (3)]

In a subsequent step, if necessary, as shown in FIG. 1C, at least the position of the mold or the processing substrate is adjusted such that the alignment marks 105 on the mold and the alignment marks 103 on the processing substrate are opposite each other. quasi.

[Irradiation step (4)]

Subsequently, the contact portion between the photocurable composition 101 and the mold 104 is irradiated with light through the mold 104 and the mold is aligned with the substrate as shown in FIG. 1D. More specifically, the coating film 106 filling the pattern in the mold 104 is irradiated with the light 107 through the mold 104 (FIG. 1D (d-1)). Thus, a portion of the coating film 106 filling the fine pattern of the mold 104 is cured by light to form a cured product 108 (Fig. 1D (d-2)).

The light of the photocurable composition 101 that irradiates the coating film 106 forming the fine pattern of the filling mold 104 is appropriately selected in accordance with the wavelength sensitive to the photocurable composition 101. Examples of such light include ultraviolet rays having 150 nm to 400 nm, X-rays, and electron beams.

Among them, ultraviolet rays are more suitable as light (illumination light 107) for irradiating the photocurable composition 101. This is because many commercially available curing agents (photopolymerization initiators) are sensitive to ultraviolet light. Light source for emitting ultraviolet light includes high pressure mercury vapor lamp, ultra high pressure mercury vapor lamp, low pressure mercury vapor lamp, deep UV lamp, carbon arc lamp, chemical lamp, metal halide lamp, xenon lamp, KrF excimer laser, ArF excimer thunder Shot, and F2 excimer laser. Ultra-high pressure mercury vapor lamps are advantageous. The number of light sources is one or two. The coating film 106 filling the mold pattern may be partially or entirely illuminated.

This irradiation can be carried out intermittently or several times continuously over the entire area of the substrate. Alternatively, the region A may be illuminated in the first phase of the illumination, and the region B different from the region A may be illuminated in the second phase of the illumination.

[Mold release step (5)]

Subsequently, the mold 104 is removed from the cured product 108. At this time, a cured product pattern 109 having a specific pattern has been formed on the substrate 102.

In the demolding step, as shown in FIG. 1E, the cured product 108 is separated from the mold 104 to produce a cured product pattern 109 having a pattern opposite to the fine pattern in the mold 104.

In the case where the mold contacting step is performed in a condensable gas atmosphere, the condensable gas evaporates as the pressure at the interface between the cured product 108 and the mold 104 is lowered by removing the mold 104 from the cured product 108. This helps to remove the mold 104 with low force.

The manner in which the mold 104 is removed from the cured product 108 (including the conditions for demolding) is not particularly limited as long as the cured product 108 is not substantially damaged. For example, the mold 104 can be moved away from the fixed processing substrate 102, or the substrate 102 can be moved away from the fixed mold 104. Alternatively, the mold 104 and the substrate 102 can be pulled in opposite directions to separate them from one another.

The above method including the steps (1) to (5) forms a cured film having a desired convex pattern derived from a convex pattern in the mold 104 at a desired position. The resulting cured film can be used, for example, as an optical member such as a Fresnel lens or a diffraction grating, or a part of such an optical member. In this example, the optical member includes at least a substrate 102 and a patterned cured product pattern 109 on the substrate 102.

In the method of the embodiment, the steps (1) to (5) are included The repeating unit (shot) can be performed several times on the same substrate 102. By repeating the repeating unit (process) including the steps (1) to (5) several times, a cured product pattern having a plurality of desired patterns based on the convex pattern of the mold 104 in the desired region can be formed.

[Removal of Partially Cured Film Unwanted Part Removal Step (6)]

The cured product pattern formed through the step (5) or the demolding step has a specific pattern, and it may remain in an area other than the region where the pattern should be formed (hereinafter, portions of the cured film may be referred to as unwanted portions) ). In this case, as shown in FIG. 1F, the unwanted portion of the cured product pattern is removed. Thus, a cured product pattern 110 having a desired pattern (formed based on the raised pattern of the mold 104) is formed.

In this step, an undesired portion of the cured film in the recess of the cured product pattern 109 can be removed by, for example, etching to expose the surface of the substrate 102 in the recess of the cured product pattern 109.

In order to remove an undesired portion of the cured product pattern 109 by etching, any technique may be applied without particular limitation, and known techniques such as dry etching may be performed. For the dry etching, a known dry etching apparatus can be used. The source gas system used for the dry etching is appropriately selected depending on the elemental composition of the cured film to be etched, and examples thereof include halogen-containing gases such as CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF ₆ , and Cl ₂ ; oxygen-containing gases such as O ₂ , CO, and CO ₂ ; inert gases such as He, N ₂ , and Ar; and H ₂ and NH ₃ . A mixed gas of these gases can be used.

In the above method including the steps of the steps (1) to (6), a cured product pattern 110 having a desired convex pattern (a convex pattern derived from the mold 104) at a desired position is formed, thus completing the formation An article that cures the product pattern. If the substrate 102 is treated with a cured product pattern 110, a processing step (step (7)) is performed on the substrate as described below.

Alternatively, the resulting cured product pattern 110 can be used as an optical member, such as a diffraction grating or polarizer, or a portion of such an optical member, as an optical component. In this example, the optical assembly includes at least the substrate 102 and a patterned cured product pattern 110 on the substrate 102.

[Substrate processing step (7)]

The cured product pattern 110 having the convex pattern formed by the method of the present embodiment can be used as an interlayer insulating film of an electronic component such as a semiconductor device, or a resist film used in a method of manufacturing a semiconductor device. Examples of such semiconductor devices include LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM.

If the cured product pattern 110 is used as a mask (resist film), the portion of the substrate that has been exposed by the step (6) (or the etching step) (the region indicated by 111 in FIG. 1F) is etched. Or ion implantation. In this example, the cured product pattern 110 acts as an etch mask. Additionally, the substrate 102 can be provided with electronic components. Thus, the circuit structure 112 is formed on the substrate 102 in accordance with the shape of the cured product pattern 110 (Fig. 1G). Thus, a circuit board for a semiconductor device or the like is manufactured. The resulting board can be connected A control mechanism that is connected to the board to manufacture electronic components of the display, camera, medical device, or other device.

Similarly, the cured product pattern 110 can be used as a mask (resist film) for etching or ion implantation in a method of manufacturing an optical component.

Alternatively, the cured product pattern 110 can be used to fabricate an imprint mold by etching a quartz substrate that is the substrate 102. In this case, the quartz substrate can be directly etched using the cured product pattern 110 as a mask. Alternatively, the hard mask material layer may be etched using the cured product pattern 110, and the quartz substrate is etched using the transfer pattern of the hard mask material as a mask. A second cured product of the second curable material may be formed in the recess of the cured product pattern 110, and the second cured product may be used as a mask for etching the quartz substrate.

In order to partially use the cured product pattern 110 as a substrate for mask etching exposure, dry etching can be applied. For the dry etching, a known dry etching apparatus can be used. The source gas system used for the dry etching is appropriately selected depending on the elemental composition of the cured film to be etched, and examples thereof include halogen-containing gases such as CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF ₆ , and Cl ₂ ; oxygen-containing gases such as O ₂ , CO, and CO ₂ ; inert gases such as He, N ₂ , and Ar; and H ₂ and NH ₃ . Fluorine-containing gas systems are suitable, such as CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₈ , CCl ₂ F ₂ , CBrF ₃ , and SF ₆ . The photocurable composition of the embodiment of the present invention is highly resistant to dry etching using such fluorine-containing gases. A mixed gas of these gases can be used.

In the method of manufacturing a circuit board or the like, the cured product The pattern 110 may eventually be removed from the treated substrate or may remain as a component of the device.

[Examples]

The invention is described in further detail with reference to the following examples. However, the invention is not limited to the following examples.

[Comparative Example 1] (1) Preparation of photocurable composition (b-1)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Comparative Example 1 (b-1). ).

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, manufactured by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 3 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 3 parts by weight

In the photocurable composition (b-1), the component (A) has an Ohnish parameter O _A of 3.53, and the component (E) has an Ohnish parameter O _E of 2.30. In the photocurable composition (b-1), the content of the component (E) was 3.1% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (b-1)

The viscosity of the photocurable composition (b-1) was measured at 25 ° C using a plate cone rotational viscometer RE-85L (manufactured by Toki Sangyo), and the result was 3.80 mPa. s.

(3) Forming a cured film of the photocurable composition (b-1)

2 μL of the light curable composition (b-1) was dropped on the tantalum wafer to provide a 60 nm thick adhesive layer as an adhesive layer. Then, the dropped photocurable composition (b-1) was covered with a 1 mm thick quartz glass to fill a square region having a side of 25 mm.

Subsequently, the coating film was irradiated with the UV light source having the ultrahigh pressure mercury vapor lamp and the light passing through the interference filter was irradiated through the quartz glass for 200 seconds. The interference filter was VPF-25C-10-15-31300 (manufactured by Sigmakoki), and the ultraviolet light for irradiation had a single wavelength of 313 ± 5 nm and an illuminance of 1 mW/cm ² .

After the irradiation, the quartz glass was removed from the coating film. Thus, a cured film having a photocurable composition (b-1) having an average thickness of 3.2 μm was formed on the tantalum wafer.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (b-1)

The cured film of the obtained photocurable composition (b-1) was dry-etched using a ULVAC high-density plasma etching apparatus NE-550 using an etching gas CF ₄ and CHF ₃ at a flow rate of 50 sccm and 50 sccm, respectively. 500 seconds. The dry etch rate (nm/s) was calculated from the thickness reduced by dry etching. The lower the dry etch rate, the higher the resistance to dry etch. The results are shown in Table 2.

[Comparative Example 2] (1) Preparation of photocurable composition (b-2)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Comparative Example 2 (b-2). ).

(1-1) Component (A): the total amount is 100 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 50 parts by weight

<A-4> Dimethylol tricyclodecane diacrylate DCP-A (product name, manufactured by Kyoeisha Chemical): 50 parts by weight

(1-2) Component (B): the total amount is 3 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 3 parts by weight

In the photocurable composition (b-2), the component (A) has an Ohnish parameter O _A of 2.94, and the component (E) has an Ohnish parameter O _E of 2.30. In the photocurable composition (b-2), the content of the component (E) was 2.9% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (b-2)

The viscosity of the photocurable composition (b-2) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 9.3 mPa. s.

(3) Forming a cured film of the photocurable composition (b-2)

A cured film having a photocurable composition (b-2) having an average thickness of 3.2 μm was formed on the tantalum wafer in the same manner as in Comparative Example 1.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (b-2)

The cured film of the obtained photocurable composition (b-2) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Comparative Example 3] (1) Preparation of photocurable composition (b-3)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Comparative Example 3 (b-3). ).

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, manufactured by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 20 parts by weight

<B-1> Irgacure 651 (manufactured by BASF): 20 parts by weight

In the photocurable composition (b-3), the component (A) has an Ohnish parameter O _A of 3.53, and the component (E) has an Ohnish parameter O _E of 2.69. In the photocurable composition (b-3), the content of the component (E) was 17.5% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (b-3)

The viscosity of the photocurable composition (b-3) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 5.3 mPa. s.

(3) Forming a cured film of the photocurable composition (b-3)

A cured film having a photocurable composition (b-3) having an average thickness of 3.2 μm was formed on the tantalum wafer in the same manner as in Comparative Example 1.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (b-3)

The cured film of the obtained photocurable composition (b-3) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Comparative Example 4] (1) Preparation of photocurable composition (b-4)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Comparative Example 4 (b-4). ).

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, manufactured by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 20 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 20 parts by weight

In the photocurable composition (b-4), the component (A) had an Ohnish parameter O _A of 3.53, and the component (E) had an Ohnish parameter O _E of 2.3. In the photocurable composition (b-4), the content of the component (E) was 17.5% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (b-4)

The viscosity of the photocurable composition (b-4) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 6.3 mPa. s.

(3) Forming a cured film of the photocurable composition (b-4)

A cured film having a photocurable composition (b-4) having an average thickness of 3.2 μm was formed on the tantalum wafer in the same manner as in Comparative Example 1.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (b-4)

The cured film of the obtained photocurable composition (b-4) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Comparative Example 5] (1) Preparation of photocurable composition (b-5)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Comparative Example 5 (b-5). ).

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, manufactured by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 8 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 3 parts by weight

<B-2>benzophenone (manufactured by Tokyo Chemical Industry): 5 parts by weight

In the photocurable composition (b-5), the component (A) had an Ohnish parameter O _A of 3.53, and the component (E) had an Ohnish parameter O _E of 2.07. In the photocurable composition (b-5), the content of the component (E) was 7.8% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (b-5)

The viscosity of the photocurable composition (b-5) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 4.1 mPa. s.

(3) Forming a cured film of the photocurable composition (b-5)

An average thickness was formed on the tantalum wafer in the same manner as in Comparative Example 1. A cured film of the light curable composition (b-5) having a degree of 3.2 μm.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (b-5)

The cured film of the obtained photocurable composition (b-5) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Example 1] (1) Preparation of photocurable composition (a-1)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Example 1 (a-1). ).

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, manufactured by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 13 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 3 parts by weight

<B-2>benzophenone (manufactured by Tokyo Chemical Industry): 10 parts by weight

In the photocurable composition (a-1), the component (A) had an Ohnishi parameter O _A of 3.53, and the component (E) had an Ohnishi parameter O _E of 2.04. In the photocurable composition (a-1), the content of the component (E) was 12.1% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (a-1)

The viscosity of the photocurable composition (a-1) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 4.3 mPa. s.

(3) Forming a cured film of the photocurable composition (a-1)

A cured film having a photocurable composition (a-1) having an average thickness of 3.2 μm was formed on the tantalum wafer in the same manner as in Comparative Example 1.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (a-1)

The cured film of the obtained photocurable composition (a-1) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Embodiment 2] (1) Preparation of a photocurable composition (a-2)

The following components (A) and (E) (or (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition (a-2) of Example 2. .

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, manufactured by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 18 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 3 parts by weight

<B-2>benzophenone (manufactured by Tokyo Chemical Industry): 15 parts by weight

The photocurable composition (a-2) had an O _A value of 3.53 and an O _E value of 2.03. In the photocurable composition (a-2), the content of the component (E) or (B) was 16.1% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (a-2)

The viscosity of the photocurable composition (a-2) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 4.4 mPa. s.

(3) Forming a cured film of the photocurable composition (a-2)

A cured film having a photocurable composition (a-2) having an average thickness of 3.2 μm was formed on the tantalum wafer in the same manner as in Comparative Example 1.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (a-2)

The cured film of the obtained photocurable composition (a-2) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Example 3] (1) Preparation of a photocurable composition (a-3)

The following components (A) and (E) (component (B)) were mixed, and the mixture was filtered with a 0.2 μm ultrahigh molecular weight polyethylene filter to give a photocurable composition of Example 3 (a-3). ).

(1-1) Component (A): the total amount is 94 parts by weight

<A-1> Isodecyl acrylate IB-XA (product name, manufactured by Kyoeisha Chemical): 9.0 parts by weight

<A-2> Benzyl acrylate V #160 (product name, manufactured by Osaka Organic Chemical Industry): 38 parts by weight

<A-3> Neopentyl glycol diacrylate NP-A (product name, by Kyoeisha Chemical): 47 parts by weight

(1-2) Component (B): the total amount is 23 parts by weight

<B-1>Lucirin TPO (manufactured by BASF): 3 parts by weight

<B-2>benzophenone (manufactured by Tokyo Chemical Industry): 20 parts by weight

In the photocurable composition (a-3), the component (A) had an Ohnishi parameter O _A of 3.53, and the component (E) had an Ohnishi parameter O _E of 2.02. In the photocurable composition (a-3), the content of the component (E) was 19.7% by weight based on the total weight of the components (A) and (E).

(2) Measuring the viscosity of the photocurable composition (a-3)

The viscosity of the photocurable composition (a-3) was measured at 25 ° C in the same manner as in Comparative Example 1, and the result was 4.6 mPa. s.

(3) Forming a cured film of the photocurable composition (a-3)

A cured film having a photocurable composition (a-1) having an average thickness of 3.2 μm was formed on the tantalum wafer in the same manner as in Comparative Example 1.

(4) Measuring the dry etching rate of the cured film of the photocurable composition (a-3)

The cured film of the obtained photocurable composition (a-3) was subjected to dry etching for 500 seconds in the same manner as in Comparative Example 1, and the dry etching rate was used as a cured film for the photocurable composition (b-1). The relative value of the dry etch rate (=100) is calculated. The results are shown in Table 2.

[Summary of Comparative Examples and Examples]

The results of Comparative Examples 1 to 5 and Examples 1 to 3 are shown together in Table 2.

The photocurable composition (b-1) of Comparative Example 1 had a low viscosity, but its dry etching resistance was low. The photocurable composition (b-2) of Comparative Example 2 (wherein the component (A) has a composition different from (b-1)) exhibited a higher dry etching than the composition (b-1) of Comparative Example 1. Resistance, while the viscosity is greatly improved.

With respect to the photocurable composition (b-3) of Comparative Example 3, the O _A -O _E value was less than 1.00, and the dry etching resistance was not greatly improved even if the ratio of the component (E) was increased. . With respect to the photocurable composition (b-4) of Comparative Example 4, the dry etching resistance was increased by the O _A -O _E value as high as more than 1.00, and the viscosity was higher than the weight average molecular weight of the component (E). 250 and improved.

With respect to the photocurable composition (b-5) of Comparative Example 5, it has an O _A -O _E value of up to more than 1.00 and wherein the component (E) has a weight average molecular weight of less than 250, dry etching resistance Increase slightly and do not increase the viscosity. However, since the ratio of the component (E) is as low as less than 10% by weight, the dry etching resistance is insufficient.

On the other hand, the photocurable compositions (a-1), (a-2) and (a-3) of Examples 1 to 3 exhibited a well-balanced satisfactory viscosity and high dry etching resistance. Therefore, it is expected that the photocurable compositions of Examples 1 to 3 can realize light nanoimprinting at high productivity and high yield.

Although the present invention has been described with reference to the exemplary embodiments, it is understood that the invention is not limited The scope of the following claims is to be accorded

101‧‧‧Photocurable composition

102‧‧‧Substrate

103, 105‧‧‧ alignment marks

104‧‧‧Mold

106‧‧·coating film

107‧‧‧Light

108‧‧‧Curing product

109, 110‧‧‧ cured product pattern

111‧‧‧ Section

112‧‧‧Circuit structure

Claims (21)

A photocurable composition comprising: a polymerizable compound (A) having at least one polymerizable functional group and having a parameter O _A =N _A /(N _C,A -N _O, A ), wherein N _A represents The total number of atoms in the molecule of the polymerizable compound (A), N _{C, A} represents the number of carbon atoms in the molecule of the polymerizable compound (A), and N _{O, A} represents a molecule in the molecule of the polymerizable compound (A) a number of oxygen atoms; and a non-polymerizable component (E) containing at least one non-polymerizable functional group and a non-polymerizable compound (X) including a photopolymerization initiator (B) in a ratio relative to the polymerizable compound (A) And the total weight of the non-polymerizable component (E) is in the range of 10% by weight to 50% by weight, the non-polymerizable component (E) has a weight average molecular weight of 250 or less, and the non-polymerizable compound (X) has The parameter O _X =N _X /(N _C,X -N _O,X ), wherein N _X represents the total number of atoms in the molecule of the corresponding compound (X), and N _{C, X} represents the molecule of the corresponding compound (X) The number of carbon atoms, and N _{O, X} represents the number of oxygen atoms in the molecule of the corresponding compound (X); wherein the photocurable composition satisfies the following relations (1) and (2): O _A -O _E > 1.00 (1); and O _AE < 3.40 (2), wherein O _E represents a molar fraction of the parameter O _X of the at least one non-polymerizable compound (X), and O _AE represents a parameter O _A and O The molar fraction of _E is a weighted average. The photocurable composition of claim 1, wherein the photocurable composition has a photo-curable composition of 1 mPa. s to 6mPa. Sticky range of s degree. A photocurable composition as claimed in claim 1 or 2 wherein the O _{E is} less than 2.20. The photocurable composition of claim 1 or 2, wherein the ratio of the non-polymerizable component (E) is based on the total weight of the polymerizable compound (A) and the non-polymerizable component (E) It is in the range of 15% by weight to 50% by weight. The photocurable composition of claim 1 or 2, wherein the non-polymerizable component (E) is non-volatile. The photocurable composition of claim 1 or 2, wherein the photocurable composition is substantially free of volatile solvents. The photocurable composition of claim 1 or 2, wherein the non-polymerizable component (E) comprises at least one compound selected from the group consisting of benzophenone, biphenyl, and couplet three benzene. The photocurable composition of claim 1 or 2, wherein the photocurable composition is used for photon imprinting. The photocurable composition according to claim 1 or 2, wherein the polymerizable compound (A) has at least one (meth) acrylonitrile group, and the non-polymerizable compound (X) does not have (meth) propylene醯基. The photocurable composition of claim 1 or 2, wherein the ratio of the non-polymerizable component (E) is relative to the total weight of the polymerizable compound (A) and the non-polymerizable component (E) A range of 16.1 to 50% by weight. For example, the photocurable composition of claim 1 or 2, Wherein the non-polymerizable component (E) contains a fluorenylphosphine-based compound as a photopolymerization initiator (B), and contains at least one compound selected from the group consisting of benzophenone, biphenyl, and a couplet Triphenyl. A method for forming a pattern of a cured product, the method comprising: a first step of applying a photocurable composition according to any one of claims 1 to 8 to a substrate; Contacting the photocurable composition with a mold; a third step of curing the photocurable composition by light to cure the photocurable composition to a cured product; and a fourth step of separating the curing after the third step The product is with the mold. The method of claim 12, wherein the sequence from the first step to the fourth step is performed multiple times on different regions of the substrate. The method of claim 12, wherein the mold has a pattern in its surface, and the third step is performed by irradiating the photocurable composition with light through the mold. The method of claim 12, wherein the second step is carried out in an atmosphere containing a condensable gas. The method of claim 15, wherein the condensable gas is 1,1,1,3,3-pentafluoropropane. A method of manufacturing an optical component, comprising: the method of any one of claims 12 to 16 The method forms a step of curing the product pattern. A method of manufacturing a circuit board, comprising: forming a cured product pattern by a method according to any one of claims 12 to 16; and using the cured product pattern as a mask on the substrate The step of etching or ion implantation is performed. The method of claim 18, wherein the etching is performed using a gas containing at least one selected from the group consisting of CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₈ , CCl ₂ F ₂ , CBrF ₃ , and SF ₆ . The method of claim 18, wherein the circuit board is used in a semiconductor device. A method of manufacturing an imprinting mold, comprising: forming a cured product pattern by the method of any one of claims 12 to 16; and etching the substrate using the cured product pattern.